Hair dyeing with substituted nitrophenylene-diamines

ABSTRACT

THE INVENTION RELATES TO PROCESSESS FOR DYEING KERATINIC FIBERS AND LIVE HUMAN HAIR WITH SUBSTITUTED NITROPHENYLENEDIAMINES.

United States Patent Ofice 3,560,136 Patented Feb. 2, 1971 US. Cl.8-10.1 Claims ABSTRACT OF THE DISCLOSURE The invention relates toprocesses for dyeing keratinic fibers and live human hair withsubstituted nitrophenylenediamines.

Products formed from nitrophenylene-diamine by substitution are wellknown active ingredients used in solutions for coloring keratinicfibers, and particularly human hair.

In order to broaden the range of shades which may be obtained, resorthas been had to dyes derived from nitroparaphenylene-diamine ornitro-ortho-phenylene-diamine by attaching to at least one of the aminegroups connected to the aromatic nucleus, a group, such as an alkylchain, comprising an extra-nuclear amine function. Dyes have also beenused in which the amine groups connected to the aromatic nucleus weresubstituted by alkyl or hydroxyalkyl radicals.

The series of derivatives produced from nitroparaphenylene-diamine makesit possible to obtain colors ranging from red to blue; the seriesproduced from nitro-orthophenylene diamine makes it possible to obtainorange shades.

Since in practice natural hair shades are obtained by mixing dyesranging from yellow to blue, it is most important to have hair dyesproducing a yellow or yellowgreen shade available.

It is the object of this invention to provide yellow dyes having a goodaffinity for keratinic fibers.

Specifically, it is the object of this invention to provide a newarticle of manufacture which consists of a chemical following formula:

in which R R R R represent an atom of hydrogen, a lower alkyl radical,or a radical corresponding to the formula:

in which R and R7 represent a hydrogen atom or a lower alkyl radical butR and K; may not represent a hydrogen atom when they are on asubstituent chain of the nitrogen atom in the para position with respectto the N0 11 represents a whole number between 2 and 6 inclusive, onlyone of the radicals R R R or R representing a radical and R representinga hydrogen atom, and lower alkyl radical.

The invention also relates to those quaternary derivatives of thecompositions according to Formula I by quaternization of theextra-nuclear amine group at the end of the chain, when said group is atertiary amine group.

The present invention is also directed to a process for preparing onecategory of chemical compositions covered by general Formula I andrepresented by general in which R R R R R R R and n have thesignificances hereinbefore assigned thereto, and especiallycharacterized by the fact that a compound having the Formula III:

R2 O2N (III) in which R R and R have the significances hereinbeforeassigned thereto and X represents a halogen atom or an N0 group, isreacted with an aliphatic diamine corresponding to the Formula IV:

in which R R R and n have the significances hereinbefore assignedthereto, said reaction taking place preferably in the presence of asolvent such as pyridine.

A further object of the present invention is to provide a process forpreparing one category of the chemical compositions covered by thegeneral Formula I and corresponding to the Formula V:

in which R R R R R and n have the significances hereinbefore indicated,said process being essentially characterized by the fact that acomposition corresponding to Formula VI:

lTIIIz N O 2 (VI) in which R has the significance hereinbefore indicatedand X represents a halogen atom, is reacted with a secondary aminehaving the Formula VII:

R (VII) in which R and R have the significances het'einbefore indicated;the primary aromatic amine is then converted into a monosubstitutedarylsulfonamide by means of an aryl sulfochloride; and that a tertiaryaliphatic halogenated amine having the Formula VIII.

R (VIII) in which Y represents a halogen atom and R R and n have thesignificances hereinbefore indicated, is condensed on an alkaline oralkaline earth derivative of said sulfonamide, after which the productobtained is subjected to acid hydrolysis, and then quaternized.

It should be noted that the quaternization of a compositioncorresponding to Formula I and having an extranuclear tertiary aminegroup is effected in the conventional way, utilizing a quaternizingagent such as an alkyl or aryl halide or methyl sulfate, in the presenceof a solvent.

Yet another object of the present invention is to provide a haircoloring composition essentially characterized by the fact that itcontains at least one dye responding to Formula I or at least one of thecorresponding quaternary compounds.

The coloring compositions according to the present invention make itpossible to produce an intense yellow, slightly greenish shade on hairtreated therewith. It should be noted that dyes corresponding to FormulaI have a strong affinity for the keratinic fibers of human hair and thatthe hair coloring compositions which are based on these dyes areparticularly resistant to shampooing, but do not color the scalp.Moreover, the shades do not change with the passage of time.

The said hair coloring compositions are simple aqueous solutions of theaforementioned dyes. No oxidizing agents need be added to develop thecolor when these coloring compositions are used. Various conventionalingredients commonly used in hair dyeing compositions, such as organicsolvents, thickening agents, detergents, perfumes, and lacquers, may beadded to the hair coloring compositions in question.

The time during which these coloring compositions are left in contactwith the hair may be varied within broad limits, but is preferablybetween 5 and 30 minutes. The temperature at which these compositionsare applied may also be varied, but in most cases, they are preferablyused at room temperature. The concentration of the dye in the haircoloring solutions may be substantially varied, but this concentrationis preferably between 0.01% and 3%.

The coloring compositions according to the invention have, in general, apH value between 4 and 10, and preferably between 7 and 9. Their pH maybe adjusted by using as an alkali either plain ammonia, or any organicbase such, for example, as an alkyl amine, an alkanol amine, or aheterocyclic amine.

It should be noted that the new dyes according to the invention may bemixed with each other and may also be mixed with other dyes, whethernitro dyes, azo dyes, anthraquinone dyes, or any of the other types ofdye conventionally used for dyeing hair.

It should also be noted that dyes according to Formula I may also beused for other than cosmetic purposes. In fact, the presence of aprimary, secondary or tertiary extra-nuclear aliphatic amine group inthe molecule of Formula -I imparts thereto a very substantial potentialreactivity which can be put to good use in various synthesizingprocesses Without being adversely afiected by the reactivities of thenuclear amines, which are greatly reduced by the presence of a nitrogroup, whether ortho or para.

The invention also relates to a method of applying hair coloringsolutions to the hair, which method comprises the steps of impregnatingthe hair with a coloring solution which is left in contact with the hairfor 5 to 30 minutes, and then rinsing and drying the hair.

Described below by way of non-limitating illustration of the inventionare several examples of preparation and use of these dyes.

EXAMPLE I Preparation of1-methy1-2-amino-4-'y-dimethylaminopropyl-amino-5-nitrobenzene There isheated for 8 hours at reflux, 0.1 mol of 1-methyl-2-amino-4-chloro-5-nitrobenzene, (that is, 18.65 g.) in 0.4 molof N,N-dimethyl-propylenediamine, (that is 40.8 g.) in the presence ofcm. of pyridine. The greater part of the pyridine anddimethyl-propylenediamine is expelled under vacuum, poured over dilutehydrochloric acid, the insoluble part is dried and the filtrate isalkalized with sodium hydroxide.

23 g. of 1-methyl-2-arnino-4-v-dimethyl-amino-propylamino-S-nitrobenzenealmost pure are obtained which after recrystallization in'alcohol meltsat 123 C.

Analysis.Calcd for C H N O (percent): C, 57.14; H, 7.93; N, 22.22. Found(percent): C, 57.10-57.29; H, 7.91-7.79; N, 22.06-22.17.

EXAMPLE II Preparation of1-methyl-2-amin0-4-[3-aminoethylarnino-S-nitrobenzene of1-methyl-2-amino-4-,B-

aminoethylamino-S-nitrobenzene, almost pure, which afterrecrystallization in alcohol, melts at 145 C.

Analysis.Calcd for C H N O (percent): C, 51.43; H, 6.66; N, 26.66. Found(percent): C, 51.21-51.33; H, 6.81-6.69; N, 26.58-26.35.

EXAMPLE III Preparation of methyl-v-[N-(2-nitro-4-methyl-5-amino)phenyl] -aminipropyltrimethylammonium sulfate 0.1 mol of1-methyl-2-amino-4-'y-dimethyl-aminopropylamino-S-nitrobenzene (that is,25.2 g.) is dissolved in 250 cm. of nitrobenzene at air temperature;0.11 mol (that is, 13.8 g.) of methyl sulfate is added.

36.8 g. of methyl-y-[N-(2-nitro-4-methyl-5-amino)phenyl]-aminopropyltrimethylammonium sulfate is obtained which meltswith decomposition at 142 C.

EXAMPLE IV Preparation of 1-amino-3--dimethylaminopropylamino-4-nitro-benzene monohydrochloride For thispreparation the reaction of the 3,4-dinitroacetanilide on an aliphaticdiamine is utilized by taking advantage of the moblity of the N grouplocated on the benzene nucleus in meta position of the acetylated amine.Then the amide function is hydrolyzed in a hydrochloric environment. 1

0.0137 mol of 3,4-dinitro-acetanilide (that is, 3.1 g.) having 140 C.fusion point is heated for an hour at reflux in 0.3 mol ofN,N-dimethyl-propylenediamine (that is, 30 g.). The excess of aliphaticdiamine is expelled under vacuum. The reactive mixture is poured into100 cm. of Water. The1-acetamino-3-N,N-dimethylaminopropylamino-4-nitrobenzene with ethylacetate is extracted and the ethyl acetate is removed under vacuum. Inthis way 3.1 g. of an oily product is obtained which is treated for ahalf-hour at reflux by 25 cm. of a hydrochloric solution 3 times normal.After cooling and neutralization at pH=6 by means of sodium hydroxidesolution times normal, 2.6 g. of monohydrochloride of 1-amino-3-'y-dimethylaminopropylamino-4-nitrobenzene is dried, and afterrecrystallization in cold water, melts with decomposition at 280 C.

Analysis of the product obtained gives the following results:

Analysis.Calcd. for C H N O Cl (percent): C, 48.09; H, 6.92; N, 20.40.Found (percent): C, 47.99- 48.18; H, 6.98-6.78; N, 20.26-20.25.

EXAMPLE V Preparation of1-N,N-dimethylamino-3-B-aminoethylamino-4-nitrobenzene 0.04 mol of3,4-dinitro-N,N-dimethylaniline (that is, 8.4 g.) is heated for an hourat reflux in 0.8 mol of the monohydrate of ethylene-diamine (that is, 65cm. The reactive mixture is left overnight at ambient temperature and 7g. of crude 1-N,N-dimethylamino-3-/8-aminoethyl amino-4-nitrobenzene isdried. This crude product, after having been carefully washed in water,is dissolved in half-normal hydrochloric acid. The hydrochloric solutionis filtered in order to eliminate a small insoluble fraction; 6.2 g. ofthe desired product is alkalized with a 10 times normal sodium hydroxidesolution and dried. This pro duct after recrystallization inisopropanol, melts at 108 C.

Analysis of the product obtained gives the following results:

Analysis.Ca1cd. for C H N O (percent): C, 53.57; H, 7.14; N, 25.00.Found (percent): C, 53.36-53.52; H, 7.21-7.24; N, 24.93-24.99.

EXAMPLE VI Preparation of 1-N,N-dimethylamino-3-y-dimethylaminopropylamino-4-nitrobenzene 0.227 mol of3,4-dinitro-N,N-dimethylaniline (that is 48 g.) is heated for 2 hours atreflux in 1.816 mol of N,N-dimethyl-propylenediamine (that is, g). Theexcess of N,N-dimethyl-propylenediamine is removed under vacuum; thereactive mixture is poured into 600 cm. of water, 56.2 g. of the crudeproduct is dried. This crude product, after having been carefully washedin water and dried, is recrystallized in cyclohexane. It melts at 79 C.

Analysis of the product obtained gives the following results:

Analysis.Calcd. for C H N O (percent): C, 58.65; H, 8.27; N, 21.05.Found (percent): C, 58.57-58.74; H, 8.30-8.11; N, 21.02-21.06.

EXAMPLE VII Preparation of methyl-y [N-(2-nitro-5-dimethylamino) phenyl]aminopropyltrimethylammonium sulfate To a solution of 0.094 mol of1-N,N-dimethylamino- 3-'y-dimethylaminopropylamino-4-nitrobenzene (thatis 25 g.) in 250 cm. of toluene is slowly added, without stirring, 0.094mol of methyl sulfate (that is, 11.85 g.).

The reactive mixture is left alone for two hours at air temperature and35.1 g. of the quaternized compound is dried. This compound, afterrecrystallization in alcohol, melts at 165 C.

Analysis of the product obtained gives the following results:

Analysis.-Calcd. for C H N O S (percent): C, 45.91; H, 7.14; N, 14.28.Found (percent): C, 4 5.95- 46.07; H, 7.00-7.02; N, 14.40-14.36.

EXAMPLE VIII Preparation of monohydrochloride of 1-N,N-dimethylamino-3-,3-diethylaminoethylamino-4- nitrobenzene 0.165 mol of3,4-dinitro-N,N-dimethylaniline (that is, 35 g.) are heated for an hourat reflux in 1.32 mol of N,N-diethyl-ethylenediamine (or 153 g.).

The excess of aliphatic diamine is removed under vacuum; the reactivemixture is poured into 450 cm. of water. After having dried andcarefully washed the crude product in water, it is dissolved in 150 cm.of normal hydrochloric acid, filtered, and the pH of the filtrate isbrought to 7 by means of a 5 times normal sodium hydroxide solution. 42g. of the monohydrochloride of 1 N,N dimethylamino 3 ,8diethylaminoethylamino-4-nitrobenzene is dried, then afterrecrystallization in alcohol, melts with decomposition between and 200C.

Analysis of the product obtained gives the following results:

Analysis.-Calcd. for C H N O Cl (percent): C, 53.08; H, 7.89; N, 17.69.Found (percent): C, 53.20- 53. 17; H, 7.63-7.71; N, 17.82-17.70.

EXAMPLE IX Preparation of the monohydrochloride of 1-N,N-diethylamino-3-'y-dimethylaminopropylamino- 4-nitrobenzene 0.074 mol of3,4-dinitro, N,N-diethylaniline (or 17.7 g.) are heated for an hour anda half at reflux in 0.6 mol of N,N-dimethylpropanediamine (or 60 g.).The excess aliphatic diamine is removed under vacuum, the reactivemixture is poured into 100 cm. of water and the awaited product isextracted with the help of isopropyl oxide. The solution of isopropyloxide is saturated with gaseous hydrochloric acid and 18 g. ofmonohydrochloride of 1-N,N-diethylamino-3-'y-dimethylaminopropylamino-4-nitrobenzene is dried, and after recrystallization in isopropanol, itmelts with decomposition at 191 C.

Analysis of the product obtained gives the following results:

Analysis.-Calcd. for C H O N Cl (percent): C, 54.16; H, 8.17; N, 16.94.Found (percent): C, 54.57- 54.69; H, 8.28-8.05; N, 17.08-17.09.

7 EXAMPLE x Preparation of 1-methyl-2-N-fl-diethylarninoethylamino-4-dimethylamino-S-nitrobenzene First phase.Preparation of1-methyl-2-amino-4- dimethyl-amino-S-nitrobenzene 0.2 mol of1-methyl-2-amino-4-chloro-5-nitrobenzene (that is, 37.3 g.) is heatedfor 16 hours at 125 C. with an aqueous solution at 40% of 1.6 mol ofdimethylamine (that is, 180 g.) in solution 185 cm. of absolute alcohol.After cooling 32 g. of l-methyl-2-amino-4-dimethylamino- S-nitrobenzenecrystallized in red needles is dried, this product afterrecrystallization in alcohol melts at 146 C.

Analysis of the product obtained gives the following results:

Analysis.Calcd. for C H N O (percent): C, 55.38; H, 6.66; N, 21.54.Found (percent): C, 55.47-55.29; H, 6.59-6.51; N, 21.27-21.31.

Second phase.-Preparation ofl-methyl-Z-benzenesulfonylamino-4-dimethylamino-5-nitrobenzene To asolution of 0.05 mol of 1 methyl-2-amino-4-di methylamino-5-nitrobenzene(or 9.75 g.) in 60 cm. of pyridine, slowly and while stirring, there isadded at 45 C., 0.075 mol of benzene-sulfochloride (that is, cm. Afterthe addition, the reactive mixture is held at 45 C. for two hours, thenit is poured over 300 g. of ice, is acidified up to pH 5 with a 5 timesnormal hydrochloric solution and the crude l-methyl2-benzenesulfonylamino- 4-dimethylamino-5-nitro-benzene is dried. Thecrude product is redissolved in 50 cm. of a 3 times normal sodiumhydroxide solution. The sodium hydroxide solution is filtered: 1.5 g. ofthe starting product insoluble in sodium hydroxide is recovered. Then g.of l-methyl-2-benzenesulfonylamino-4-dimethylamino 5 nitrobenzene isobtained after neutralizing by hydrochloric acid and drying. It melts at130 C.

Third phase-Preparation of the1-methyl-N-benzenesulfonyl-2-N-[3-diethylaminoethylamino-4-dimethylamino-S-nitrobenzene 0.02 mol of1-methyl-2-benzenesulfonylamino-4-dimethylamino-S-nitrobenzene (or 6.7g.) is dissolved in a boiling bath of 35 cm. of dimethylformamide.0.0206 mol of potassium hydroxide (or 1.22 g.) in solution in 7.7 cm.alcohol is added, then quite rapidly 0.0204 mol of,8-diethylaminoethylchloride (that is, 2.76 g.) is added. The reactivemixture is kept for half an hour in a boiling water bath, poured intocm? of water, and the expected productis decanted under the form oforange oil which is purified by dissolving in 50 cm. of a 5 times normalhydrochloric solution and by reprecipitation by means of a sodiumhydroxide solution. Thus there is obtained 7 g. of1-methyI-Z-N-benzenesulfonyl-N-B-dimethylaminoethylamino-4-dimethylamino-5-nitrobenzene.

Fourth phase.Preparation ofI-methyI-Z-N-B-diethylaminoethylamino-4-dimethylamino-5-nitrobenzeneSlowly, while stirring, 0.06 mol of l-methyl-N-benzenesulfonyl 2 N [idiethylaminoethylamino 4 dimethylamino-S-nitrobenzene (or 29.6 g.) isintroduced into 70 cm. of concentrated sulfuric acid between 0 and 5 C.The reactive mixture is let alone for four hours at 0 C.; then it ispoured over 500 g. of ice, is alkalinized with a 4 times normal sodiumhydroxide solution, the expected product is extracted by means of ethylacetate and the solvent is removed under vacuum. The oily residue ismade into a solution in 60 cm. of ethyl acetate. After having saturatedthe iced alcoholic solution with dry gaseous hydrochloric acid, 20 g. ofdihydrochloride of 1- methyl 2 N ,8 diethylaminoethyl amino 4dimethylamino 5 nitrobenzene is dried, and melts with decomposition atC. The base, separated from its hydrochloride in the customary fashion,is an orange oil.

EXAMPLE XI Preparation of methyl-B-[N-(3-dirnethylamino-4-nitro-6-methyl)phenyl] aminoethyl methyldiethylammonium sulfate This quaternarycompound is prepared by quaternization with methyl sulfate from thecompound obtained as indicated in the Example X.

0.049 mol of 1-methyl-2-N-fl-diethylaminoethylamino-4-dimethylamino-5-nitrobenzene (or 14.5 g.) is dissolved in 120 cm. ofchlorobenzene at air temperature. 8 cm. of methyl sulfate is slowlyadded while stirring and the reactive mixture is left for twenty hoursat ordinary temperature. 18 g. of the awaited quaternary is dried, andmelts with decomposition at 153 C.

Analysis of the product obtained gives the following results:

Analysis.Calcd. for C H N SO (percent): C, 48.58; H, 7.61; N, 13.34.Found (percent): C, 48.6548.75: H. 7.84-7.78; N, 13.0913.30.

EXAMPLE XII The following solution is prepared:

l-methyl-2-amino-4-'y-dimethylamino-propylamino- 5-nitrobenzene0.2 g.

Lauric alcohol condensed with 10.5 mol of ethylene oxide4 g.

Water, q.s.p.100 cm.

This solution has a pH of 9. It is applied to 100% white hair for tenminutes at ordinary temperature. Then the hair is rinsed and shampooed;a yellow shade is obtained.

9 EXAMPLE XIII The following solution is prepared:

Methyl-'y- 2-nitro-4-methyl-5-amino -phenyl]aminopropyltrimethylammonium sulfate1.9 g.

Laurie alcohol condensed with 10.5 mols of ethylene oxide5 g.

CO Na two times normal q.s.p.-pH=l Water, q.s.p.-10O cm This solution isapplied for 10 minutes on 100% white hair at ordinary temperature. Thenthe hair is rinsed and shampooed; a yellow shade is obtained, moresustained (lasting) then in Example XII.

EXAMPLE XIV The following solution is prepared:

1-methyl-2-amino-4-fl-aminoethylamino-5-nitrobenzene-0.25 g.

Laurie alcohol condensed with 10.5 mols of ethylene oxide g.

Water, q.s.p.-100 cm.

This solution is applied on 100% hair for minutes. After rinsing andshampooing a very strong yellow green is obtained.

EXAMPLE XV The following solution is prepared:

1-methyl-2-amino-4- 3-aminoethylamin0-5-nitrobenzene-0.042 g.

Dihydrochloride of 1-N-B-aminoethylamino-Z-nitro-4-N-di-B-hydroxyethylaminoben2ene-0.252 g.

Laurie alcohol condensed with 10.5 mols of ethylene oxide4 g.

CO Na twice normal q.s.p.pH=9

Water, q.s.p.100 cm.

This solution is applied for 10 minutes on 100% white hair. Afterrinsing and shampooing a chestnut brown is obtained.

EXAMPLE XVI The following solution is prepared:

1-methyl-2-aminc-4w-dimethylaminopropylamino- 5-nitrobenzene--0.025 g.

Dihydrochloride of 1-N-[i-aminoethylamino-Z-nitro-4-N'-di-fl-hydroxyethylaminobenzene0.288 g. Laurie alcohol condensedwith 10.5 mols of ethylene oxide4 g. CO Na twice normal q.s.p.pH=7Water, q.s.p.100 cm.

This compound is applied to 100% white hair for minutes. The hair isrinsed and shampooed. A light gray beige is obtained (light naturalgray).

EXAMPLE XVII The following solution is prepared:

Methyl-'y- [N- 2-nitro-4-methyl-5-amino) -phenyl]aminopropyltrimethylammonium sulfate-0.266 g.

Monohydrobromide of 1-N-methylamino-2-nitro-4-N-B-aminoethylaminobenzene-O.435 g.

Laurie alcohol condensed with to 10.5 mols of ethylene oxide1.5 g.

CO Na twice normal q.s.p.pH=9

Water, q.s.p.100 cm.

This compound is applied to hair of light chestnut to dark blond; it isleft for 10 minutes; then hair is rinsed and washed. A strong mahoganychestnut is obtained.

EXAMPLE XVIII The following coloring compound is prepared:

1-N,N-dimethylamino-3-/3-aminoethylamino-4-nitrobenzene0.2 g.

Laurie alcohol condensed with 10.5 mols of ethylene oxide2 g.

5% solution of citric acid q.s.p.pH=7

Water, q.s.p.l00 g.

This compound is applied to dark blond hair; it is left to act for 10minutes, the hair is rinsed and washed. A bronze reflection is obtained.

EXAMPLE XIX The following coloring compound is prepared:

l-N,N-dimethylamino-3-'y-dimethylaminopropylamino- 4-nitrobenzene0.40 g.

Laurie alcohol condensed with 10.5 moles of ethylene oxide-2 g.

5% solution of citric acid, q.s.p.-pH=7 Water, q.s.p. g.

This solution is applied to chestnut hair, it is left for 10 minutes,rinsed and washed. A golden chestnut is obtained.

EXAMPLE XX The following coloring solution is prepared:

Methyl-' [N- 2-nitro-5-dimethylamino phenyl]aminopropyltrimethylammonium sulfate0.37 g.

Laurie alcohol condensed with 10.5 mols of ethylene oxide--2 g.

Sodium carbonate twice normal solution, q.s.p.pH=9

. Water, q.s.p.l00 g.

This compound is applied to light chestnut hair; it is allowed to actfor 10 minutes, rinsed and washed by shampooing. A dull gold reflectionis obtained.

EXAMPLE XXI The following coloring solution is prepared:

1 N,N dimethylamino-3-' -dimethylaminopropylamino- 4-nitro benzene-023g.

Monohydrobromide of 1-N-methylamino-2-nitro-4-N'43-aminoethylaminobenzene1.16 g.

Laurie alcohol condensed with 10.5 mols of ethylene 0xidel g.

Sodium carbonate twice normal solution, q.s.ppH=9 Water; q.s.p.-100 g.

This solution is applied to light chestnut hair; it is left for 10minutes, rinsed, and shampooed. A mahogany chestnut is obtained.

EXAMPLE XXII The following coloring solution is prepared:

This solution is applied to 100% White hair; it is left for 15 minutes,rinsed, and shampooed. A flat ash blond is obtained.

EXAMPLE XXIII The following coloring solution is prepared:

Methyl-' [N- (2-nitro, S-dimethylamino phenyl]-aminopropyltrimethylammonium sulfate0.20 g. Monohydrobromide of1-N-methylarnino-2-nitro-4-N'-flaminoethylaminobenzene0.35 g.

Lauric alcohol condensed with 10.5 mols of ethylene oxide4 g.

Sodium carbonate, twice normal solution, q.s.p.pH=7

Water, q.s.p.100 g.

This mixture is applied to light chestnut hair; it is left for minutes,rinsed, and washed. A light chestnut with slight violine light isobtained.

EXAMPLE XXIV The following coloring solution is prepared:

Monohydrochloride of l-amino 3 'ydimethylaminopropylamino-4-nitrobenzene0.23 g.

Lauric alcohol condensed with 10.5 mols of ethylene oxide-3 g.

Sodium hydroxide solution, 5 times normal, q.s.p.--

Water, q.s.p.-100 g.

This mixture is applied to light chestnut hair; it is left for minutes,Washed, and rinsed. A light golden chestnut is obtained.

EXAMPLE XXV The following coloring solution is prepared:

Monohydrochloride of1-N,N-diethylamino-3-y-dimethylaminopropylamino-4-nitrobenzene0.26 g.

Lauric alcohol condensed with 10.5 mols of ethylene oxide-3.5 g.

20% citric acid solution, q.s.p.pH-=8 Water, -q.s.p.-100 g.

This mixture is applied to light chestnut hair; it is left on for 10minutes, rinsed and washed. A bronze high light is obtained.

EXAMPLE XXVI The following coloring solution is prepared:

Monohydrochloride of1-N,N-diethylamino-3-y-dimethylaminopropylamino-4-nitrobenzene0.05 g.

Monohydrobromide of .1-N-methylamino-2-nitro-4-N'-methyl-N'-fl-aminoethylaminobenzene0.20 g.

Laurie alcohol condensed with 10.5 mols of ethylene oxide-2.5 g.

Sodium carbonate, twice normal solution, q.s.ppH=8 Water; q.s.p.100 g.

This mixture is applied to 100% white hair; it is left on for minutes,rinsed and washed by shampooing. A light mahogany is obtained.

EXAMPLE XXVII The following coloring solution is prepared:

Monohydrochloride of1-N,N-dimethylamino-3-fl-diethylaminoethylamino-4-nitrobenzene0.32 g.

Laurie alcohol condensed with 10.5 mols of ethylene oxide4 g.

Sodium carbonate, twice normal solution, q.s.p.-pH=7 Water, q.s.p.-l00g.

This mixture is applied to light chestnut hair; it is left for 10minutes, rinsed, and washed by shampooing. A dull gold light isobtained.

EXAMPLE XXVIII The following coloring solution is prepared:

Monohydrochloride of1-N,N-dimethylamino-3-,8-diethylaminoethylamino-4-nitrobenzene0.062 g.Monohydrobromide of 1-N-,8-aminoethylamino-Z-nitro-4-N,N-fl-hydroxyethylaminobenzene0.188 g. Sodium carbonate, twice normalsolution, q.s.p.pH=7 Water, q.s.p.100 g.

This solution is applied to 100% white hair; it is left for 15 minutes,rinsed and shampooed. An ash blond is obtained.

12 EXAMPLE XXIX The following coloring solution is prepared:

Methyl-fl-[N-(3-dimethylamino 4 nitro 6 methyl)-phenyl]-aminoethyl-methyldiethylammonium sulfate- 2 g. Laurie alcoholcondensed with 10.5 mols of ethylene oxide-5 g.

CO Na twice normal, q.s.p.pH=10 Water, q.s.p.-100 cm? This solution isapplied for 10 minutes to 100% white hair at ordinary temperature. Thenthe hair is rinsed; it is washed by shampooing; a sustained yellow shadeis obtained.

EXAMPLE XXX The following coloring solution is prepared:

Methyl-,B-[N-(3-dimethylamino 4 nitro 6- methyl)-phenyl]-aminoethyl-methyldiethylammonium sulfate- 0.067 g.

Dihydrochloride of 1-diethylaminoethylamino-2-nitro-4-N,N-dihydroxyethylaminobenzene0 .328 g.

Iso-octylphenyl-polyethoxyethanol4 g.

Water, q.s.p.100 g.

This mixture is applied to white hair; it is left for 15 minutes; it isWashed and rinsed. A light chestnut is obtained.

It is understood that various changes, improvements, or additions can bemade in the preparation and examples of application which have just beendescribed, or certain products may be replaced by equivalent products,without changing the general nature of the invention.

What is claimed is:

1. A process for tinting keratinic fibers and live human hair whichcomprises applying to said fibers and said hair a coloring amount of adyeing composition comprising an aqueous solution containing a coloringamount of a dye compound selected from the group consisting of acompound having the formula:

N R3 R4 in which R R R R are selected from the group consisting ofhydrogen, lower alkyl and in which R and R are selected from the groupconsisting of hydrogen and lower alkyl, R and R not being capable ofrepresenting a hydrogen atom when they are on a substitute chain of thenitrogen atom placed in para position of the N0 group, n represents anumber between 2 and 6, and R is selected from the group consisting ofhydrogen and lower alkyl, and quaternary ammonium salts of said compoundobtained by quaternization of the tertiary extra-nuclear amine group.

2. The process of claim 1, in which said dye compound is selected fromthe group consisting of l-methyl-2-amino-4,-dimethylaminopropylamino-5-nitrobenzene,

1-methyl-2-amino-4-fi-aminoethylamino-5-nitrobenzene,

methyl-y- [N-(2-nitro-4-methyl-5-amino)phenyl]-aminopropyltrimethylammonium sulfate,

l-an1ino-3-'y-dimethylaminopropylamino-4-nitrobenzene monohydrochloride,

1-N,N-dimethyla1nino-3-,8-an1inoethyl-amino-4-nitrobenzene,

1-N,N-dimethy1amino-3-' -dimethylaminopropylamino- 5. The process ofclaim 1, wherein the concentration of 4-nitrobenzene, said dye isbetween 0.01% and 3%. methyl-y [N-2-nitro-5-dimethylamino phenyl]-aminopropyltrimethylammonium sulfate, References Cited1-N,N-dimethylamino-3-;8-diethylaminoethylamino-4- 5 UNITED STATESPATENTS nitrobenzenc hydrochloride, 1-N,N-diethylamino-3-'-dimethylaminopropylamino-4- fi g 3 3 nitrobenzene hydrochloride, o r ea 1-methyl-2-II-B-diethylaminoethylamino-4-dimethyl- FOREIGN PATENTS and1 237,199 12/1964 Austria s .11

methyl-fi- [N-(3-dirnethy1amino-4-nitro-6-methy1)phenyl]aminoethylmethyldiethyl ammonium sulfate. ALBERT MEYERS Prlmary Exammel3. The process of claim 1, wherein the dyeing composi- CLARKE AssistantExaminer tion has a pH between 4 and 10.

4. The process of claim 3, wherein said pH is be- 15 tween 7 and 9. 8l0;260-5675, 570.5

